Mono- and disazo dyes and the 1:1 and 1:2 metal complexes thereof containing one or more thiosulfate groups

ABSTRACT

AZO DYES AND 1:1 AND 1:2 METAL COMPLEXES THEREOF ARE DISCLOSED, SAID DYES BEING CHARACTERIZED IN HAVING IN THEIR MOLECULES AT LEAST ONCE THE RADICAL OF   R1-NH-X-SSO3Z   WHEREIN X IS PHENYLENE, ETHYLENE, PROPYLENE,   -(1,3-PHENYLENE)-CH2-   IN WHICH THE -CH2-IS BONDED TO THE -SSO3Z, CHLOROPHENYLENE IN WHICH THE CL IS ORTHO TO THE -SSO3Z, METHOXPHENYLENE IN WHICH METHOXY IS META TO THE -SSO3Z,   -(1,4-PHENYLENE)-SO2-NH-CH2-CH2-   IN WHICH A METHYLENE IS BONDED TO THE -SSO3Z, OR   -(1,3-PHENYLENE)-SO2-NH-CH2-CH2-   IN WHICH A METHYLENE IS BONDED TO THE -SSO3Z; Z IS H, NA OR K; AND R1 IS 8-HYDROXY-6-SULFO-2-NAPHTHYL, 5HYDROXY - 7 - SULFO - 2-NAPHTHYLS, 6,8-DISULFO-2-NAPHTHYL, 5,7 - DISULFO - 2 - NAPHTHYL, 6-SULFO-2-NAPHTHYL, 8-SULFO2-NAPHTHYL, 5-SULFO - 2 - NAPHTHYL, 8-HYDROXY-4,6-DISULFO1-NAPHTHYL, 7-SULFO - 2-NAPHTHYL, OR 4-SULFO-1-NAPHTHYL. THE DYES ARE PARTICULARLY USEFUL FOR MAKING WET-FAST DYEINGS ON COTTON AND REGENERATED CELLULOSE TEXTILE FABRICS.

United States Patent 3,562,246 MONO- AND DISAZO DYES AND THE 1:1 AND 1:2 METAL COMPLEXES THEREOF CONTAINING ONE OR MORE THIOSULFATE GROUPS Frederick E. Barwick IH and Gordon A. Geselbracht,

Charlotte, N.C., assignors to Martin Marietta Corporation, a corporation of Maryland No Drawing. Filed Sept. 25, 1967, Scr. No. 670,435 Int. Cl. C09b 29/24, 45/14, 45/24 US. Cl. 260148 Claims ABSTRACT OF THE DISCLOSURE Azo dyes and 1:1 and 1:2 metal complexes thereof are disclosed, said dyes being characterized in having in their molecules at least once the radical of R NHXSSO Z wherein X is phenylene, ethylene, propylene,

NaOrSSONH- in which the CH is bonded to the SSO Z, chlorophenylene in which the Cl is ortho to theSSO Z, me thoxyphenylene in which the methoxy is meta to the in which a methylene is bonded to the SSO Z, or

I SOzNHCHzCHi in which a methylene is bonded to the -SSO Z; Z is H, Na or K; and R is 8-hydroxy-6-sulfo-2-naphthyl, 5- hydroxy 7 sulfo 2-naphthyls, 6,8-disulfo-2-naphthyl, 5,7 disulfo 2 naphthyl, 6-sulfo-2-naphthyl, 8-sulfo- 2-naphthyl, 5-sulfo 2 naphthyl, 8-hydroxy-4,6-disulfol-naphthyl, 7-sulfo 2-naphthyl, or 4-sulfo-1-naphthyl. The dyes are particularly useful for making wet-fast dyeings on cotton and regenerated cellulose textile fabrics.

The present invention relates to azo dyestuffs.

Generally speaking, the azo dyestuffs of the present invention are particularly characterized in that they are dyestuffs selected from the group consisting of:

/R4-NHXSSO:Z D4

(d) 1:1 copper, 1:1 cobalt, 1:1 chromium, 1:1 nickel,

3,562,246 Patented Feb; 9, 1971 1:1 iron, 1:2 chromium, 1:2 cobalt, or 1:2 nickel complex compounds of an azo dye of the formula (e) 1:1 copper, 1:1 cobalt, 1:1 chromium, 1:1 nickel, of 1:1 iron complex compounds of an azo dye of the formula D -RNHXSSO Z,

taneous reaction of 1 molecular proportion of an azo dyestuif of the formula 1 atomic proportion of Co, and 1 atomic proportion of Cr, said reactants being in solution; wherein:

D is a radical of a diazo compound of the benzene or naphthalene series connected to a ring C of R by an azo group of said radical of the diazo compound;

X is phenylene, ethylene, propylene,

in which the CH is bonded to the -SSO Z, chlorophenylene in which the Cl is ortho to the -SSO Z, methoxyphenylene in which the methoxy is meta to the in which a methylene is bonded to the -SSO Z, or

l S OzNHCHzCHr- 3 ene (2), 7-sulfo 1,2 naphthylene (1), or 4-sulfo 1,2- naphthylene (2);

D is the radical of a diazo compound of the benzene or naphthalene series having a metallizable substituent on an aromatic portion thereof, a ring C atom of which aromatic portion is linked to a ring C atom of the adjoining naphthylene radical via an azo group of the radical of the diazo compound, and in which the metallizable substituent is located ortho to said azo group;

R is 1 hydroxy 3 sulfo-2,7-naphthylene (2), 1- hydroxy-3-sulfo-2,6-naphthylene (2), 8 hydroxy 4- sulfo 1,7 naphthylene (7), or 8 hydroxy-4,6-disulfo- 1,7-naphthylene (7);

D is the radical of a diazo compound of the benzene series connected to a ring C of R by an azo group of said radical of the diazo compound, said radical of the diazo compound being further characterized in having an aromatic portion bearing two metallizable substituents ortho to each other;

R is 8-hydroxy-6-sulfo 1,2 naphthylene (1), 5- hydroxy 7 sulfo 1,2 naphthylene (1), 8-hydroxy- 4-sulfo-1,2-naphthylene (2), 5-sulfo 1,2 naphthylene (1), or 4-sulfo-1,2-naphthylene (2) N=N-YN= is the radical of a tetrazotized diaminodiphenylsulfone, diaminodiphenylether, diaminodiphenylsulfide, diaminodiphenylmethane, diaminodiphenyl, or 4,4'-or 3,3'-diaminodiphenyldisulfide;

N:NY -N=N is the radical of a tetrazotized diaminodiphenylsulfone, diaminodiphenylether, diaminodiphenylsulfide, diaminodiphenylmethane, diaminodiphenyl, or 4,4'- or 3,3-diaminodiphenyldisulfide, said radicals being further characterized in that phenyl rings thereof adjoining the azo group linked to R have a metallizable substituent bonded to a ring O atom of said phenyl rings, said metallizable substituent being located ortho to the azo group linked to R D and D each represent a radical of a diazo compound of the benzene or naphthalene series connected to a ring C of R, by an azo group of said radical of the diazo compound; and

R is 5 hydroxy 7 sulfo-1,2,6-naphthalenetriy1 (1) (6), 8 hydroxy 4 sulfo-1,2,7-naphthalenetriyl (2) (7), or 8 hydroxy 4,6 disulfo 1,2,7-naphthalenetriyl (2) (7), and in which the numbers within parentheses following each naphthalenetriyl radical indicate the positions of the naphthalenetriyl radical to which the azo groups of D and D are attached;

D is a radical of a diazo compound of the benzene or naphthalene series having a metallizable substituent on an aromatic portion thereof, a ring C atom of which aromatic portion is linked via an azo group of the radical of the diazo compound to the ring C atom of R located ortho to the OH substituent R and in which the metallizable substituent is located ortho to said azo group;

D is a radical of a diazo compound of the benzene or naphthalene series connected to a ring C atom of R by an azo group of said radical of the diazo compound;

R is 5-hydroxy-7-sulfo-1,2,6-naphthalenetriyl (1), 8- hydroxy-4-sulfo-1,2,7-naphthalenetriyl (2), or 8-hydroxy- 4,6-disulfo-1,2,7-naphthalenetriyl (2), and in which the number in parenthesis following each naphthalenetriyl radical indicates the position of the naphthalenetriyl radical to which the azo group of D is attached; and further characterized in that the number within parenthesis following each naphthylene radical indicates the position of the naphthylene radical to which the adjoining azo group is attached.

The dyestuffs of the present invention are particularly suitable for making wet fast dyeings on cotton and regenerated cellulose textile fabrics by the dyeing method described in Belgian Pat. No. 681,524.

It is surprising and unexpected that the dyestuffs of the present invention may be prepared, because one with skillin the art would expect the notoriously labile thiosulfate group of the naphthyl-thiosulfate intermediates used in making the dyes to hydrolyze when said intermediates are synthesized, because of the reaction conditions. It is particularly surprising that the dyestufis of the present invention are useful in making dyeings which are fast to wet treatments, as the thiosulfate group promotes solubility in water, and the present dyestuffs have, in addition to one or more thiosulfate groups, one or more sulfonic acid groups, which sulfonic acid groups are known to promote strongly solubility in water. Excessive numbersof water solubilizing groups on a dye molecule are customarily believed to render the dye non-fast to wet treatments and washing, and to render the dye tinctorially weak. It is therefore surprising that the present dyes have good wash fastness. Moreover, many of the dyes of the present invention have surprisingly strong tinctorial power.

The present invention is of particular value in contributing to greater flexibility in the thiosulfate dye making art. For example, it has been known in the prior art to couple one or two moles of diazotized aminophenylthiosulfates with a mle of a naphthol to make thiosulfate dyes (Canadian Pat. No. 754,555, issued Mar. 14, 1967). However, in that case the diazo coupling component was necessarily restricted to aminophenylthiosulfates. One

' advantage of the present invention is that one preparing thiosulfate dyes may now select ay desired diazo coupling component for coupling with the naphthyl-thiosulfate intermediates used herein, unlimited by whether or not the diazo contains a thiosulfate group; accordingly, a broad range of diazo compounds, and those known to have good fastness properties, may now be employed.

The process by which the dyes of the present invention are prepared readily lends itself to commercial adaptation, in that the materials are easy to handle, simple and inexpensive plant equipment may be used, and there are no difiicult separation steps.

Generally speaking, the dyes of the present invention may be prepared as follows.

Dyes of the formula DR-NHXSSO Z, wherein D, R, X and Z are as above defined, may be prepared by coupling equimolar amounts of a diazotized amine (diazotized azoic base) of the benzene or naphthalene series and a compound of the formula R NHX-SSO Z,

under alkaline or acid conditions, wherein X and Z are as above defined and R is 8hydroxy-6-sulfo-2-naphthyl, 5-hydroxy-7-sulfo-Z-naphthyl, 6,8-disulfo-2-naphthyl, 5- 7-disulfo-2-naphthyl, 6 sulfo 2 naphthyl, 8-sulfo-2- naphthyl, 5-sulfo-2-naphthyl, 8-hydroxy-4,6 disulfo-1- naphthyl, 7-sulfo-2-naphthyl, or 4-sulfo-1-naphthyl. Although these couplings proceed under acid or alkaline conditions, better yields result if the naphthyl-thiosulfate compounds without an OH substituent are coupled under acid conditions. In some of the foregoing naphthylthiosulfate compounds, whether the compound is coupled under acid or alkaline conditions determines the position at which the azo of diazotized amine attaches to the naphthyl radical to form the resulting naphthylene radical. For example, when the coupling is under alkaline conditions, the following first named naphthyl radical forms into the following second named naphthylene radical, and the azo coupling is at the position of the naphthylene radical indicated by the number in parenthesis following the naphthylene radical: 8-hydroxy-6-sulfo-2-naphthyl into l-hydroxy-3-sulfo-2,7-naphthylene (2), 5-hydroxy-7 sulfo-Z- naphthyl into 1-hydroxy-3-sulfo 2,6 naphthylene (2), 8-hydroxy-4-sulfo-l-naphthyl into 8-hydroxy-4-sulfo-1,7- naphthylene (7 8-hydroxy-4,6-disulfo-1-naphthyl into 8- hydroxy-4,6-disulfo-l,7-naphthylene (7); under acid conditions 8hydroxy-6-sulfo-2-naphthyl into 8 hydroxy-G- sulfo-1,2-naphthylene (1), S-hydroxy-7-sulfo-2-naphthyl into 1hydroxy-3-sulfo-2,6-naphthylene (2), 8-hydroxy-4- sulfo-l-naphthyl into 8-hydroxy-4-sulfo-1,Z-naphthylene (2), 8-hydroxy-4,6-disulfo-1naphthyl into 8-hydroxy-4,6- disulfo-1,2-naphthylene (2); and whether coupled under acid or alkaline conditions 6,8-disulfo-2-naphthyl into 6,8-

disulfo-1,2-naphthylene (1), 5,7-disulfo-2 naphthyl into 5,7-disulfo-1,2-naphthylene (1), 6-sulfo-2-naphthyl into 6-sulfo-l,2-naphthylene (2), 8-sulfo-2 naphthyl into 8- sulfo-1,2-naphthylene (1), 5-sulfo-2-naphthyl into 5-sulfo- 1,2-naphthylene (1), 7-sulfo-2-naphthyl into 7-sulfo-1,2- naphthylene (1), and 4-sulfo-1-naphthyl into 4-sulfo1,2- naphthylene (2).

A20 dyestuffs of the formula may be prepared by coupling, under acid or alkaline conditions two molecular proportions of and one molecular proportion of a tetrazotized diamine selected from the group of diamines consisting of diaminodiphenylsulfones, diaminodiphenylethers, diaminodiphenylsulfides, diaminodiphenylmethanes, diaminodiphenyls, 4,4-diaminodiphenyldisulfides, and 3,3'-diaminodiphenyldisulfides, wherein Z, X, R, Y, and R are as above defined.

Azo dyestuffs of the formula \R 4-NHXSS Z Dr may be prepared by coupling under acid conditions equimolar proportions of a diazotized amine of the benzene or naphthalene series and a compound of the formula R NHX--SSO Z to produce a monoazo dyestuif, and coupling under alkaline conditions equimolar proportions of the resulting monoazo dyestutf and a diazotized amine of the benzene or naphthalene series, wherein D D R X, and Z are as above defined and R is S-hydroxy- 7-sulfo-2-naphthyl, 8-hydroxy-4-sulfo-1 naphthyl, or 8- hydroxy4,6-disulfo-l-naphthyl. In the acid coupling step of this process, the azo group attaches to the 1 position of the 5-hydroxy-7-sulfo-2-naphthyl, and to the 2 position of the 8-hydroxy-4-sulfo-l-naphthyl and the 8-hydroxy- 4,6-disulfo-'l-naphthyl. In the alkaline coupling step of this process, the azo group attaches to the 6 position of the former 5-hydroxy-7-sulfo-2-naphthyl, and the 7 position of the former 8-hydroXy-4-sulfo-l-naphthyl and the former 8-hydroxy-4,6-disulfo-l-naphthyl.

The dyestuffs of the present invention which are metal complex compounds may be prepared as follows:

1:1 copper, 1:1 cobalt, 1:1 chromium, 1:1 nickel, or 11 iron complex compounds of an azo dye of the formula D RNHX-SSO Z, D 'R NH-X-SSO Z may be prepared by heating at about pH 67.5 an aqueous composition of a molecular proportion of one of the above dyes with an atomic proportion of an aqueous solution of Cu, Cr, Co, Ni, or Fe per azo group to be bridged by the metal atom, said metals being a solution of their soluble salts.

1:2 chromium, 1:2 cobalt, or 1:2 nickel complex compounds of an azo dye of the formula D -R NHX-SSO Z may be prepared by heating at about pH 6-7.5 an aqueous compositions of a molecular proportion of a dye of the formula D -R --NH-XSSO Z with 0.5 atomic proportion of an aqueous solution of Cr, Co or Ni, said metals being a solution of their soluble salts.

In the foregoing metallization processes, reaction will usually be complete when the composition has been heated 2-8 hours at 75100 C.

As used herein, the term 1:1 metal complex indicates one metal atom for each azo group of the dyestuif molecule which is bridged by the metal atom, and 1:2 metal complex indicates 1 metal atom covalently bound to 2 azo groups, which azo groups may be located in the same dye molecule or in 2 diiferent dye molecules.

The above dyestuffs which are to be metallized may be prepared in their non-metallized state as follows, following Which they Will be metallized.

The dyestufi of the formula may be prepared by coupling, under alkaline conditions, equimolar amounts of R NHX-SSO Z and a diazotized amine of the benzene or naphthalene series having a metallizable substituent on an aromatic portion thereof located ortho with respect to the azo group, wherein D R Z, and X are as above defined and R7 is 8-hydroxy-6-sulfo 2 naphthyl, 5-hydroxy-7-sulfo-2- naphthyl, 8-hydroxy-4-sulfo 2 naphthyl, or 8-hydroxy- 4,6-disulfo-2-naphthyl, whereby the azo of the diazotized amine attaches to the ring C of the naphthyl ring ortho to the OH substituent of the naphthyl.

Dyes of the formula D RNHXSSO Z may be prepared by coupling under acid or alkaline conditions equimolar amounts of R --NH-XSSO Z and a diazotized amine of the benzene series which has on an aromatic portion thereof of two metallizable substituents located ortho to each other, wherein D R, X, Z and R are as above defined. In the metallization of the metal atom is covalently bound to atoms of D Dyes of the formula D -R NHX--SSO Z may be prepared by coupling, under acid conditions, equimolar amounts of R -NH--X-SSO Z and a diazotized amine of the benzene or naphthalene series having a metallizable substituent on an aromatic portion thereof located ortho with respect to the azo group, wherein D R X and Z are as above defined and R is '8-hydroXy- 6-sulfo-2-naphthyl, 8-hydroxy-7- sulfo 2- naphthyl, 8- hydroxy-4-sulfo-l-naphthyl, 5-sulfo 2 naphthyl, or 4- sulfo-l-naphthyl. The azo group of the dime compound attaches to the 2 position of 8-hydroxy-4-sulfo-1- naphthyl and 4-sulfo-1-naphthyl, and to the 1 position of the remaining R naphthyls. In the metallization of D R --NH-XfiSSO Z, the metal atom is covalently bound to a metal atom of D and to N of the -NH-.

Dyes of the formula \R5-NH-XS s OaZ 136 may be prepared by coupling under acid conditions equimolar proportions of R NHXSSO Z and a diazotized ami-ne of the benzene or naphthalene series to produce a monoazo dyestulf, and coupling under alkaline conditions equimolar proportions of the resulting monoazo dyestuifs and a diazotized amine of the benzene or naphthalene series having a metallizable substituent on a C atom of an aromatic portion thereof located ortho to the azo group, wherein D D R X, Z and R are as above defined. The azo groups attach during the azo and alkaline couplings to the R naphthyls at the positions indicated above under the method for making Dyes of the formula NR NH-X-SSO Z may be prepared by coupling under alkaline conditions two molecular proportions of R Nl-I-XSSO;,Z and one molecular proportion of a tetrazotized diamine selected from the group of diamines consisting of diaminodiphenylsulfones, diaminodiphenylethers, diaminodiphenylsulfides, diaminodiphenylmethanes, diaminodiphenyls, 4,4'-diaminodiphenyldisulfides, and 3,3-diaminodiphenyldisulfides, said tetrazotized diamines being further characterized in that each of the phenyl rings adjoining the azo groups have a metallizable substituent bonded to a ring C atom of said phenyl rings and located ortho the adjacent azo group, wherein Z, X, R

and R are as above defined.

may be prepared by coupling under alkaline conditions 1 molecular proportion of R NHXSSO Z, 1 molecular proportion R NHX-SSO Z, and one molecular proportion of a tetrazotized diamine as defined in the foregoing paragraph.

The complex metal compound resulting from simultaneous reaction of 1 molecular proportion of an azo dyestuff of the formula NaOzSS-O-HN- 1 atomic proportion of Co, and 1 atomic proportion of Cr, said reactants being in solution, may be prepared by coupling under aqueous alkaline conditions 1 molecular proportion of tetrazotized 4,4-dihydroxy- 3,3-diminodiphenylsulfone and 2 molecular proportions of NaO S- and heating for 8 hours at 90 C. and pH 7 an aqueous solution containing 1 molecular proportion of the resulting dye, 1 atomic proportion of Co as CoSO -7H O, and 1 atomic proportion of Cr as chromium acetate monohydrate.

Metallizable substituents are well known in azo dye chemistry, and illustrative examples of those suitable for use herein are --OH, COOH, and -OCH COOH.

The following is a more detailed description of the present invention.

Illustrative and non limiting examples of diazotizable amines of the benzene series suitable for use herein are aniline, or mor p-nitroaniline, m-chloroaniline, 4- amino-S'-chloro-o-benzanisidide, 4-amino 3 methoxydiphenylamine, and

Qnnso:

in which I is hydrogen, halogen, lower alkyl, lower alkoxy, or phenoxy, I is a metallizable substituent such as -OH, -COOH, or -OCH COOH in ortho position to the NH and I is located para or meta to the NH and is H, halogen, lower alkyl, or lower alkoxy.

Illustrative and nonlimiting examples of diazotizable amines of the naphthalene series suitable for use herein are l-naphthylami-ne, 1-amino-2-methoxynaphthalene, 1- amino-4-sulfonamidonaphthalene, and

The R -NHX--SSO Z intermediates used herein may be prepared as follows, wherein R X and Z are as above defined. Compounds of the formula may be prepared by heating at 60-105 C. for 12-60 hours an aqueous composition comprising approximately equimolar proportions of H N-XSSO Na and an acid selected from the group consisting of Gamma, Dioxy J acid, J acid, Dioxy S acid, Amino G acid, Amino J acid, Broenners acid, Crocein acid, D acid, K acid, F acid, and Naphthionic acid, 3.5-7 molecular proportions NaHSO per molecular proportion of H N-X-SSO Na about 0.11 molecular proportions Na CO per molecular proportion of NaHSO cooling to 0-25 C.; acidifying with 32% aqueous HCl to pH 3 while maintaining NiLOaS-- 0-25 C.; evacuating substantially all S0 gas at 025 C.; collecting the resulting precipitated product by filtration; washing free of mineral acid with 20% aqueous NaCl; and drying at 5060 C. At this stage, the R --NHX-SSO H is in acid form, and it may be converted to the corresponding R -NHX-SSO Na or R -NH-XSSO K by stirring the EXAMPLE 1 The compound of the formula may be prepared as follows.

Charge 1 liter H O at 40 C. into a 5-liter 3-neck flask. Mix therein by stirring 1,140 gms. NaHSO Add gradually during 30 minutes 119 gms. Na CO Heat to 50 C. Add 361 gms. 7-amino-1-naphthol-3-sulfonic acid. Add thereto 367 gms. sodium S-4-aminophenylthiosulfate.

HOaS- Heat the composition gradually over two hours until it reaches gentle reflux (102-105 C.), and hold at gentle reflux for 48 hours. Remove the heat source and stir to room temperature. Cool externally with an ice bath to 10 C. While maintaining 10 C., add 700 gms. 32%

10 may be prepared as follows. This example is the same as Example 1 above, except that 361 gms. 6-amino-1- naphthol-B-sulfonic acid is substituted for the 7-amino-1- naphthol-3-sulfonic acid used in Example 1, and except that 90 gms. 50% aqueous NaOH is substituted for the aqueous HCl dropwise, resulting in pH 3. Stir 12 hours 119 gms. Na CO employed in Example 1. Yield is 75% at 5-9 C. to permit substantially all S0 gas to be of theory.

liberated; collect the precipitated product by filtration; EXAMPLES 4-57 wash the product free of mineral acidity by flooding the In the exam ples given 1n the following table, the profilter cakefm vaclium fi tlmeslglth 7112 cedure corresponds to that given under Example 1 above, ous q i y W t gg er and the examples in the table indicate that 6.68 g. M.W. cake c-Yle i g f f "3 50 NaHSO is stirred into one liter H 0 at 40 c., to which Analyslimaiy be f f il e Pm is gradually added 0.74 g. M.W. Na CO and the compostandardlzed tetrazome enzl sition heated to 50 C., whereby a composition buffered EXAMPLE 2 at pH 6.2 results. One g. M.W. of the acid in the second column is added, following which 1 g. M.W. of the thio- The compound of the formula sulfate in the third column is added. The composition OH is brought gradually, over a period of about 2 hours, to I gentle reflux and there held 12-60 hours, and preferably NHC SSOaNa about 48 hours, until the condensation reaction is substantially complete. The heat source is removed and the NaOaS- composition stirred until it reaches room temperature, following which it is cooled externally to 10 C. While may be prepared by adding 150 ml. 5% NaOH to 42.7 mtaintaining 10 C., enough 32% aqueous HCl is added gms. of the compound of Example 1, stirring 15 minutes to bring the pH to about 3, and the composition is stirred at 25 C., adding 100 gms. 20% aqueous NaCl and colat about 5 C. until substantially all the S0 gas has been lecting the resulting precipitate by filtration. liberated. The resulting precipitate is recovered by filtra- EXAMPLE tion, washed with 20% aqueous NaCl at 20 C. until free of mineral acid, and dried at 50-60 C., resulting in The compound of the formula the product of the fourth column. The percent theoretical OH yield is given in the fifth column. Trivial names of the sulfonic acids in the second column have been used for convenience, and the corresponding systematic names may be found at Lubs, supra, pp. 83,689-690, and at Venka- EO taraman, The Chemistry of Synthetic Dyes, Academic Press, New York, N.Y., vol. 1, p. 171 (1952).

Ex. I Percent No. Acid Thiosuliate Product yield Saeid HzN-O-SSOsNa Hois s-O-my on 63 5 D acid Same as above T0 11 52 H038 SOME-(n 70 6 Dioxy .1 acid do L Q O S 3 orr HOaS s s 03H 61 7 Amino G acid BEN- 3 I S s OaNa 65 8--. Bmenners acid Same as above EX. Percent No. Acid Thiosulfate Product yield 9 Dioxy S acid Same as above S 0 H 63 I in SSOaH 10- F acid ..do 51 HOgS- NH 11-- Naphthionic acid ..d0 0 H 42 l NH- S S OaH 12--..- J acid II2N- HOaS S S S OaNa NH 5 03H 13. Amino J acid Same as above S 0 H 52 HOaS S NH s 03H 14.-." Crocein acid do SCIhH 47 S S 03H 3 15"... Kacid do 53 HOaS S I S 03H 16..-. Naphthionic acid. d0 44 S SOaH l7-.-.. Jacid HzNCHzCH2SSO3Na 54 HO3S S CHz -NH SO3H Ex. Percent No. Acid Thiosuifate Product yield 18 S acid Same as above 48 I S 0 H NH CH2- S S 0 H 19"-.. Amino G acid ..do /z 51 HOsS I 20- Dioxy S acid H2NCH2CH2SSO3Na (I) 62 21. K acid Same as above 3 HO3S 22 DioxyJ' acid do 51 HO3S- NH CHz S S0311 23 Aminoii acid H2NCH2 3SSO3N8 49 H035 S CH NH -S 03H -S 03H 24... Gamma acid Same as above 0 Hogs S- CHQNH- 25-.-" .1 acid .do 42 H035 S OHz NH S 0 H I 2s.-.- s acid H2NC HOQS s GHQ 64 l CH2S S OaNa 27 K acid Same as above -51 OH 57 l H023 S-CHz I S OaN Ex. Percent N0. Acid Thiosulfate Product yield 28 DloxyJ acid Same as above HO S NH- CHBS S 03H 29-.-" Facld d0 H0 8 NH 51 30 Dioxy S acid do 59 HO l |IH OHgS S 0 H 31.. D acid do S 03H 54 CHQS S 0 11 32..." Broenners acid do 57 Ho s- CHzS S 0 H 33.-. Amino J acid .do s 0 H 43 HOaS- NH-C CHzS S 03H 34"-.. Gamma acid ('31 OH ('31 74 mN-O-s s OaNa NH S s 03H 35-.... J acid Same as above (1)11 76 I 1103s SQNH s 03H 36 S acid do (I71 68 1103s s-O-mw 11 I S 0 H l 31.--. Amino G ma "do. 1103s SNH 8. Acid Thiosulfata Product $21 5 38. Amino J acid Same as above 0 H 51 01 E038 -NHC S S Call 39 Crocein acid d0 S 03H ('31 47 NH-OS s 0311 40"... Dioxy I acid ..do (3H 75 01 1103s SO-NH SOaH 41.. Gamma acid (fCHa OH 71 H2N SSO3Na NH SS03H 110 S 0 CH 42... J acid Same as above (RH 74 (EH 0 1101s S --NH s 03H 43.-... D acid $0311 52 ()OHa H038 SNH 44.-." Naphthionic acid. fin S 0 H 41 1 TH SSOsH 45"-.. Broenners acid do H03S (R0113 54 .NH SS03H 46"..- Dioxy S acid ..do NH SSO3H 67 I 1 0 CH 47-.. Croecin acid. fin 5 3 47 gD-NH-Q-Ssofii 48.-- F acid HzN 49 s ommcfimssoma It will be noted that in the foregoing examples the acid form of the sulfonic acids have been employed as starting materials; however, the corresponding sodium or potassium salt form of said sulfonic acids may be substituted therefor to produce the same products produced in the above examples. Also, the end products produced in the above examples are in their acid form, and they may be converted to their sodium or potassium salt form by the method previously described above.

The thiosulfate compounds used in the above examples to prepare the above compounds may be prepared by known methods as follows. One g. M.W. of 4,4'-diaminodiphenyldisulfide (U.S. Pat. No. 1,933,217) 3,3'-diaminodiphenyldisulfide (Beil. vol. 13, p. 426), 2,2-diaminodimay be prepared as follows:

1 g. M.W. of 3-chloroaniline is diazotized in known manner by adding 1 g. M.W. 3-chloroaniline to 2,500 ml.

phenyldisulfide (Chem. Ab. 28: p. 489 4,4'-diamino water at 25 C., adding thereto 225 gms. concentrated 2,2-dichlorodiphenyldisulfide (Chem. Ab. 51: p. 16435c), HCl at room temperature with stirring, heating the mixor 4,4-diamino-3,3'-dimethoxydiphenyldisulfide (Chem. ture to 60 C .and stirring until solution results, cooling Ab. 22: 1965 may be heated with 4 g. M.W. sodium the solution to 0 C. and holding at that temperature sulfite, and 3,500 ml. water at 75 C., while maintaining while a slight excess of NaNO as shown on starch-KI pH 7-8 with acetic acid, until the reactants are in solupaper, is added thereto with stirring. A slight amount of tion (about 48 hours) to cleave the disulfide molecule sulfamic acid is added to remove the excess NaNO A between the S atoms and produce 2 molecules of the solution of diazotized 3-chloroaniline results. corresponding sodium S-2- or -3- or -4-aminophenylthio- Equimolar proportions of the diazotized 3-chloroaniline sulfate, sodium S-4-amino-2-chlorophenylthiosulfate, or and the product of Example 1 above are coupled as folsodium S-4-amino-3-methoxyphenylthiosulfate; and they 25 lows. l g. M.W. of the product of Example 1 is dissolved may be recovered from solution by evaporating to dryin 2,000 ml. water; cooled to 5 C.; the above solution ness or salting out with NaCl. The following thiosulfate of diazotized 3-chloroaniline is added thereto; the solution compounds may be produced according to the reference is adjusted to pH 3.5 with dropwise addition of 20% cited after each one: aqueous sodium acetate during a period of 1 hour while H NtCH -l ssO Na (Chem. Ab. 47: p. 6860b); maintaining the solution at 510 C. Stir for 12 hours, H N(CH SSO Na (Chem. Ab. 48: p. 114850); while allowing the temperature of the composition to rise Sodium S-3-aminobenzylthiosulfate [1. Chem. Soc. vol. to 20 C., and recover the resulting solids. The product 93, p. 1404 (1908), and U.S. Pat. No. 3,151,144]; and is reddish-orange dyestuff in the form of the thiosulfuric acid. The thiosulfuric acid form of the dye may be con- O verted to its corresponding SSO Na form by slurrying jg the thiosulfuric acid form of the dye in water, renderlng slightly alkaline with NaOH or Na CO and the (Belgian Pat 644,759). :-SSO Na form of the dye may be recovered by evaporatmg to dryness or saltmg out with excess 20% aqueous NaCl and recovering by filtration. The SSO K form of the dye may be prepared in similar manner by substituting KOH or K CO for the above NaOH and Na CO and KCl for the above NaCl.

2 EXAMPLES 59-68 b 1 In the examples given in the following table, the prof Y b P ii gi g 3 2 F g l lfii 1 cedure is similar to that of Example 58, and the examples P a P on ammoe y 9 in the table indicate that 1 g. M.W. of the diazotizable func fis g g i li g g amine in the second column is diazotized and coupled 1r as a 1 11- 3, an fen ergng t e at about pH 3.5 with the thiosulfuric acid intermediate result alkahne.wlth a S lg t exces? of O at 25 indicated in the third column to produce the azo dyestuff The followmg examples lnustratlve of preparing shown in the fourth column, which has the shade shown the dyes of the present invention. in the fifth column Ex. No. Diazotizable amine Thiosulfuric acid .Azo dyestufi Shade 69 Red KB Product of Ex. 12 above-.. OH Orange.

HOgSS NH S 03H Ex. N0. Diazotizable amine Thiosulfurie acid Azo dyestufi Shade 60 Red RC Product of EX. 9 above S 0 H Red.

m Scarlet G Product of Ex. 19 above.-- N02 Orange;

-NIE[OH2CHs-S SOaII 62 Scarlet R...- Product of Ex. 23 above..... S 0 11 Do;

HOaSS CH2 NH- -s 03H O CH;

63 Rod FG. Product of Ex. 32 above..... D0:

C1 41H: S S OaH 64 1-naphthy1amine.-.- Product of Ex; 39 above..-.- N Do;

ojmgm i! 65 l-amino-Z-methoxy- Product of Ex; 43 above. S Do;

naphthalene.

H03 S S NH Diazotizable Ex. No. amine 'llriosulfuric acid Azo dyestuft Shade 66 l-amino i- Product of Ex. 54 above..." S O2NI'l- OH2 S S H Red.

sulfonamidol naphthalene. O

NH- HO -N=N S OzNHz 67 Black K Product of Ex. 48 above"..- (])OH3 Brown.

| IlOa S NII 0 0113 l S O2N1-I OHz S S 0311 A 68 Aniline Product of Ex. 11 above 03H Yellow.

I S S 0311 EXAMPLE 69 liter Water and 1 kg. ice by stirring. Cool to C. and The dyestuff of the formula add the above solution of diazotized o-anisidine during 1 40 hour while maintaining the composition at 5 C. Stir 12 (I311 hours While permitting temperature to rise to C. Re-

cover the product by filtration. A brown dyestulf results. N=N -NH SS OaNa EXAMPLES 70-72 NaOaS- may be prepared as follows.

1 g. M.W. of o-anisidine is diazotized by adding 1 g. M.W. of o-anisidine to 1,500 ml. Water at C., adding thereto 225 gms. concentrated HCl at room temperature with stirring, cooling to 0 C. and holding at that temperature while a slight excess of NaNO is added thereto with stirring. A solution of diazotized o-anisidine results.

Equimolar proportions of the diazotized o-anisidine and the product of Example 2 above may be coupled as follows. 1 g. M.W. of the product of Example 2 above and 1,200 ml. 20% aqueous Na CO are dissolved in 1 In the examples given in the following table, the procedure is similar to that of Example 69 above, and the examples in the table indicate that l g. M.W. of the diazotizable amine in the second column is diazotized and coupled at about pH 8.59.5 with the sodium or potassium salt form (SSO Na or -SSO K) of the thiosulfuric acid intermediate indicated in the third column, to produce the azo dyestulf shown in the fourth column, having the shade shown in the fifth column. When the K salt form of the thiosulfuric acid is employed in the process, K 00 will be substituted for the Na- CO of Example 69.

Ex. No. Diazotizable amine Thiosulfate Azo dyestufi Shad 70 Scarlet GG Na salt of product of Ex. 12 above"... OH IO1 Orange NaO3SS GH2- -NH SO3Na o1 71 l-Naphthylamine.-. K salt of product of Ex. 26 above Red;

K0 8 S CH2 -N= I S 03K if 27 Y 28 Dlazotizable Ex. No. amine Thiosulfate Azo dyestuff Shade 72 Violet B Na salt of product of Ex. 15 above- Red.

HN 011 on8 NaOaSS N=N NH(|3O S OaNa Ha IS O3N8 EXAMPLE 73 thereto during a period of 1 hour, and while maintaining The dyestuff of the formula 15 10 12 C., 1 g. M.W. diazotized 4-ni tro-2-aminophenol at 5 C. Stir 12 hours wh1le permitting the tempera- OH HO ture to rise to -25 C. Recover the resulting dyestutf solids by filtration. The diazo dyestuff is violet. -N=N 01 If desired, the above SSO Na form of the dye may I 20 be converted to its SSO H form by rendering the dye OzN NaOaS- NHC SSO3NQ slightly acid with 5% aqueous HCl at 20 C., and washing with 20% aqueous NaCl until free of mineral acid. EXAMPLES 74-75 In the examples given in the following table, the promay be prepared as f llow cedure is similar to that of Example 73, and the examples 1 g, M,W of 4-nitroaniline is diazotized by adding the in the table indicate that 1 g. M.W. Of the diazotizable same to 1,000 ml. H O at 25 C., adding 225 gms. conamine in the second column is diazotized and coupled at centrated HCl at room temperature with stirring, heating about pH 3.5 with the thiosulfuric acid intermediate indithe mixture to 75 C. and stirring until solution results, c ed in he third column to produce a monoazo dyestuif, cooling to 0 C. and there holding while a slight excess which monoazo dyestu is Coupled at about P of NaNO is added thereto with stirring. A small amount With 1 g- 0f the (halo resulting from dialoilill'ng the of sulfamic acid is added to remove the excess NaNO diazotizable amine in the fourth column to produce the resulting in a solution of diazoti d 4-nit i1in azo dyestutf shown in the fifth column, having the shade Equimolar proportions of the diazotized 4-nitroaniline shown in the sixth column.

Diazotizable 'Ihiosulfuric Dlazotizable Ex. No. amine acid amine Azo dyestufi Shade 74 Aniline Na salt of Anthranilie Black. product of acid. NH- S S O Na Ex. 4 H0 0 0 HO above. 1

l S OzNfl 75 l-naphth l- Ksalt of 5-11 drox -2'- Black.

amine. product of niethox y- NH C H S S 0 31 Ex. 21 sulfanil- 0011 HO HO )2 above. anilide. I l

and the product of Example 35 above are coupled as EXAMPLE 76 follows. 1 g. M.W. of the product of Example 35 is dissolved in 2,000 ml. H O, cooled to 5 C., and the above The azo dyestutf of the formula (|)H C1 01 OH 3 3 N&O SS-CHz-NH N=N S S N=N NH-CHz-SS OaNa A A SO3N3 NaOaS- solution of diazotized 4-nitroaniline is added. The solumay be prepared as follows.

tion is adjusted to pH 3.5 with dropwise addition of 20% 70 A solution of tetrazotized 4,4'-diamino-2,2'-dichloroaqueous sodium acetate during 1 hour while maintaining diphenyldisulfide is prepared by adding 0.1 g. M.W. 4,4- 5l0 C. Stir 12 hours while allowing the temperature diamino2,2-dichlorodiphenyldisulfide to 300 ml. water to rise to 20-25 C., thereby producing a monoazo dye. at C., adding gms. concentrated HCl at 25 C. Render the composition about pH 8.5-9.5 by adding 2,400 with stirring, heating to C. and stirring until in soluml. of 20% aqueous Na CO and cool to 10 C. Add 7 tion. Cool to 0 C. and hold at 0 C. while a slight excess The following metallizations with Cu, Co, Cr, Ni and Fe are conducted at pH 6-7.5, and those with Cu may be conducted strongly alkaline.

EXAMPLE 91 The violet dyestufl? of the formula NaOa S may be prepared as follows; 1 g. M.W. of the dyestulf of Example 69 is added to 10 liters H and heated to 80 C. To it is added a copper sulphate solution which has been prepared by dissolving 249.71 gms. copper sulphate pentahydrate in 4 liters H O at 90 C. and cooling to 25 C. The result is heated at 60 C. for 2 hours, and the dyestulf separates on salting with NaCl.

EXAMPLE 92 The azo dyestuif of the formula 9 -H1y 0' 0 NaOaS s N=N -NHC 0 s OaNa (3H3 OaNa may be prepared by adding 10 liters water to the dyestuff of Example 72 above, heating to 80 C., adding 281.1 gms. CoSO -7H O dissolved in 3 liters water, and heating at 80 C. and pH 7 for 2 hours. The dyestuff separates on salting with NaCl and is blue.

EXAMPLE 93 The dyestuff of the formula EXAMPLE 94 The azo dyestufif of the formula may be prepared by coupling under alkaline conditions, 1 g. M.W. diazotized anthranilic acid and 1 g. M.W. of the K salt of the product of Example 26 above to produce an unmetallized monoazo dye, adding 1 g. M.W. of the 36 resulting unmetallized dye to 10 liters water, heating to 0., adding 262.85 gms. NiS O .6H O dissolved in 3 liters H 0, and heating at 80 C. for 2 hours at pH 7. The dyestutf separates on salting with KCl and is violet.

EXAMPLE The azo dye of the formula N=N ssoaNa HzN 02S S O3Na may be prepared by coupling 1 g. M.W. diazotized 2- aminophenol-4-sulfonamide and 1 g. M.W. of the Na salt of the product of Example 9 above at pH 8.5-9.5; adding to 1 g. M.W. of the resulting unmetallized monoazo dyestuff solids 10 liters water and 161.21 gms. FeCl dissolved in 3 liters water; heating to 80 C.; and holding at 80 C. for 2 hours while maintaining pH 7 by adding NaOI-I as needed. The metallized dyestulf separates on salting with NaCl and is brown.

EXAMPLE 96 The azo dye of the formula l S OsNa may be prepared by coupling, under acid conditions, 1 g. M.W. of the product of Example 38 above and 1 g. M.W. diazotized to form an unmetallized dyestuff, and 1 g. M.W. of the resulting dyestuif solids is stirred in 10 liters water at 50 C., and a slight excess over 1 g. M.W. CuSO -5H O, dissolved in 1 liter water, and 300 gms. sodium acetate are added. The composition is heated at 60 C. for 1 hour; the resulting dye precipitates and is black.

EXAMPLE 97 The 1:1 cobalt analog of the metallized dye of Example 96 may be prepared by metallizing 1 g. M.W. of the unmetallized dye of Example 96 by the metallization method described in Example 92 above, except that the heating to metallize is at 95 C. instead of 80 C. The dye is brown.

EXAMPLE 98 The 1:1 chromium analog of the metallized dye of Example 96 may be prepared by metallizing 1 g. M.W. of the non-metallized dye of Example 96 by the metallization method described in Example 93 above, except that the heating is at 95 C. instead of 80 C. The dye is violet.

EXAMPLE 99 The 1:1 nickel analog of the metallized dye of Example 96 may be prepared by metallizing l g. M.W. of the non-metallized dye of Example 96 by the metallization method described in Example 94 above. The dye is violet.

37 EXAMPLE 100 The 1:1 iron analog of the metallized dye of Example 96 may be prepared by metallizing 1 g. M.W. of the non-metallized dye of Example 96 by the metallization method described in Example 95 above. The dye is brown.

EXAMPLE 101 The dyestuff of the formula may be prepared by adding 10 liters water at 80 C. to 1 g. M.W. of the dyestuff of Example 65, adding 281.1 gms. CoC .7H O dissolved in 3 liters water, and heating at pH 6.2-6.7 for hours at 90 C. The dye may be salted out with NaCl and is brown.

EXAMPLE 102 The dyestuff of the formula HOaSS- H O N (I) l s 03H may be prepared by adding 10 liters water to 1 g. M.W. of the dyestuff of Example 60 and heating to 80 C. To it is added a copper sulfate solution which has been prepared by dissolving 249.71 gms. copper sulfate pentahydrate in 4 liters water at 90 C. and cooling to C. Heat the composition at 60 C. and pH 6.5 for 4 hours. The dye may be salted out with NaCl and is brown.

EXAMPLE 103 The dyestufi of the formula may be prepared by coupling, under acid conditions, 1 g. M.W. of the product of Example 22 above and 1 g. M.W. diazotized 1 amino 4 sulfonamido 2 naphthol to form an unmetallized monoazo dye, adding 1 g. M.W. of the resulting dye solids to 10 liters water at 75 0., adding 594 gins. of a 50% aqueous solution of chromium acetate monohydrate, and heating 4 hours at C. and pH 6.26.7. The dye precipitates on salting with NaCl and is violet.

EXAMPLE 104 The dyestuif of the formula may be prepared by coupling, under acid conditions, 1 g. M.W. of the product'of Example 56 and 1 g. M.W. diazotized 4-nitro-2-aminophenol to produce a monoazo dyestuff, adding 1 g. M.W. 0f the dyestuif solids to 10 liters water, heating to 80 0, adding 262.85 gms. NiSO -6H O dissolved in 3 liters water, and heating at 80 C. for 6 hours at pH 6.26.7. The metallized dyestuff separates on salting with NaCl and is violet.

EXAMPLE 105 The dyestuff of the formula may be prepared by coupling, under acid conditions, 1 g. M.W. of the product of Example 34 above and 1 g. M.W. diazotized to form a monoazo dye, adding 1 g. M.W. of the resulting dye solids to 10 liters Water, adding 162.21 gms. FeCl dissolved in 3 liters water, and heating 10 hours at 75 C. and pH 6.47. The metallized dye separates on salting with NaCl and is brown.

39 may be prepared as follows. The process is the same as that in Example 92 above, except that the amount of CoSO -7H O is reduced to 140.55 gms. The dye is brown.

EXAMPLE 107 The dyestulf of the formula SOsN& Cl

C1 NaOaS- may be prepared as follows. The process is the same as that of Example 93 above, except that the amount of 50% aqueous solution of chromium acetate monohydrate is reduced to 297 gms. The dye is blue.

EXAMPLE 108 The dye of the formula S OaK may be prepared as follows. This process is the same as that of Example 94 above, except that the amount of KOsSS CH2 NiSO '6H O is reduced to 131.43 gms. The dye is violet.

EXAMPLE 109 The black dyestulf of the formula S O3Nii may be prepared as follows. 1 g. M.W. of the dyestuff I 0 I x x 40 of Example 74 is added to liters water at 60 C. To it is added 594 gms. of a 50% aqueous solution of chromium acetate monohydrate, and the composition is heated at 80 C. for 2 hours at pH 7. The dyestuif separates on salting with NaCl.

EXAMPLE 110 The black dyestutf of the formula NH CHZ- S S 03K OCH;

may be prepared as follows. 1 g. M.W. of the dyestuff of 'Example 75 above is added to 10 liters water and heated to C. To it is added 262.85 gms. NiSO -6H O dissolved in 3 liters H O. The composition is heated at 80 C. for 2 hours. The dyestuff separates on salting with NaCl.

EXAMPLE 111 The brown dyestulf of the formula maybe prepared as follows. 1 g. M.W. of the dyestulf of Example 73 above is added to 10 liters water and heated to 80 C. To it is added 281.1 gms. CoSO -7H O dissolved in 3 liters water, and the result heated to 80 C. for 2 hours. The dyestuff separates on salting with NaCl.

EXAMPLE 112 The black dyestuff of the formula NH SSOaNa S OaNa 

